Vat and s



retem dhu v, 1 934 var nun snnrnna nrns'rurr rnnraaanon Hermann Berthold and Erwin Liese, Level-insenasslgnors to General Germany Aniline Works, Inc., New York, N. Y. a corporation of Delaware No Drawing. Application August 14, 1933, Serial In Germany 10 Claims.

The present invention relates to a process of printing textile fibres with vat or sulphur dyestufls and to new vat and sulphur dyestuff preparations suitable for textile printing.

In accordance with the invention vat and sulphur dyestufl! preparations are produced comprising thionyldiglycol of the probable formula:--

'onioinon The new preparations are employed for the printing or slop-padding of animal-, vegetable or artiflcial fibres, such as cotton, viscose, wool, cellulose acetate silk and the like. They possess considerable advantages over the preparations hitherto known for said purpose.

Thus the new preparations ensure animproved fixing and stronger printings than the corresponding printing preparations without the addition of thionyldiglycol. Furthermore, fabrics printed with our new preparations can be stored for a prolonged time before the steaming process without any damage. Also, the finished printing colors containing 'thionyldiglycol are very stable. In consequence of these facts the printer is allowed to perform the single steps of printing (preparation of the printing paste, printin steaming and developing of the printings) with any desired interruption as is generally not the case when printing with the printing colors hitherto known.

The thionyldiglycol may be added to the dry dyestuils, whereby dry and easily workable dyestuif preparations are obtained. It may likewise be added to aqueous pastes of the vat or sulphur dyestufls with or without the addition of other ingredients used in textile printing (glycerine, hydrotropic agents etc.) or to the printing pastes at any desired stage of their manufacture.

The extent of the effect attainable does not only depend on the nature of the dye'stuif employed, but also on themethod, by which the printing colors are produced from the dyestufi preparations and on the special methods of printing. The printing methods principally concerned can be divided into two groups:

(1) Process of printing with previous reduction (known process), for example:

40-200 grams of dyestuii (in paste) are pasted with 50 grams of glycerine, 315-350 grams of water, 25-50 grams of caustic soda solution (40 B.), 20-40 grams of calcined sodium carbonate August 26, 1932 and 500-450 grams of a thickening agent, containing in 1000 parts by weightz-Q v 1 Parts by weight British gum 7 Star 100 Sodium saltof benzylsulphanilic acid 20 water toe and at 10 C. 40-90 grams of sodium formaldehyde sulphoxylate and 10-40 grams of sodium hydrosulphite are added. With this printing color textile products are printed in the customary manner, the printings are steamed, for example, in a Mather-Flatt apparatus and developed and finished in the customary manner.

When the above printing colors contain thicnyldiglycol, there are obtained stronger printings and better fixation than without these materials. The process of printing with previous reduction is generally used for dyestuffs,- which vat with difiiculty and when applying the dyestuffs in powder form. However, endeavours are made to replace this process even in the latter casw by process 2 (below)- g (2) Process of printing without previous reduction. The following is an example of the process:-

A printing color is made up from:-10-20 grams of dyestuil paste, 0-10 grams of water, grams of a thickening agent, containing in 1000 parts by weight:-

Parts by weight Tragacanth 65:1000 1'10 Industrial gum 1:1 160 Wheat star 60 Water British g 60 Glycer ne 10g Potassium carbonate 150 Sodium formaldehyde sulfoxylate 150 Textile products printed with such. printing colors are steamed in order to develop the dyeioo stuff, then oxidized and. finished in the customary manner. i

When the above printing colors contain thionyldiglycol the printings in accordance with this process are usually stronger and fix better than without this addition. Consequently, it is possible to print by this latter process also such dyestufis, which, hitherto yielded satisfactoryresults only in the first process. This i'act constitutes a considerable technical advance particularly in the avoidance of caustic alkalies, in m dextrine or of an emulsify n consequence whereof the fibre is more cautiously treated, furthermore, in the prolonged stability and applicability of the made up printing pastes in consequence of the absence of the readily decomposable hydrosulphite, which is entirely replaced by sodium formaldehyde sulphoxylate.

It should'be pointed out that these two main groups oi printing methods are likely to be applied with success in most cases, however, modiflcations of these processes are also applicable.

As already outlined above the addition of thionyldiglycol can be carried out at any desired stage of the manufacture. of the printing colors, for example:- i

(a) The dyestuif in the form of a pressed cake containing water (12-40% dyestuif content), is stirred with an aqueous solution of thionyldiglycol, if desired, in the presence of glycerine or some other similar polyhydric water soluble alcohol. After milling and sieving of the mixture, uniform, smooth pastes are obtained, which do not dry up, do not form encrustations, do not deposit, do not freeze and, even after a prolonged period, can ing colors, especially, when a preserving agent is added to the pastes.

(b) The dvestufl. is finely ground and intirmately mixed with the likewise finely ground thioof an emulsifying dinylglycol. The addition agent may be of advantage.

(0) The dyestuil' in the form of a pressed cake containing water-or in the form of an aqueous paste is evaporated to dryness in the presence of thionyldiglycol and, 'if desired, in the presence of agent.

(11) The dyestufl is reduced, advantageously by means of a hydrosulphite, in the presence of glycerine or another similar polyhydric alcohol, miscible with water, for example, thiodiglycol, thiodiglycerol' or the like, with previous, simultaneous orsubsequent addition of thionyldiglycol.

- (e) The direct addition of thionyldiglycol to the'printing color is likewise capable of considerably improving the printing qualities of the printing colors in question, for example:-

72 grams of a thickening containing in 1000 parts by weight:-

Parts by weight Wheat starch v Water 142 British gum 60 Industrial gum 1:1 260 Tragacanth :1000 170 Potassium carbonate 150 Sodium formaldehyde sulphoxylate 150 are stirred to a printing color with an aqueous dyestufl paste and 8 grams of glycerine and 8 grams of thionyldiglycol.

In all the instances described under (a) to (e) dyestuff preparations are obtained, which either as such possess technical advantages (see, for example, the preparations under (a) or, as contrasted with the same preparations without the addition of the thionyldiglycol, display improved qualities of printing and fixation.

The amount of thionyldiglycol to be added may vary within the widest limits. Generally, we prefer to apply about 50 to about by weight of the same (calculated on the dyestuif present) in order to get the best results, but substantially smaller or larger amounts are likewise operable.

If desired. additions known to favorably instill be worked up to valuable print- I fluence the printing 1 in many instances still further improved.

It should be mentioned that, when using in the claims the expression "vat and sulphur dyestuif preparations for textile printing, it is intended to .include all preparations specified under (a) to (e) and preparations similar thereto, which can find application for printing purposes and contain thionyldiglycol.

The printing methods, which can be used with advantage, have already'been considered. The development of the printings can be carried out by the customary processes, for example, in the following manner:

After drying the printed material, the same is subjected tothe action of moist steam and the dyestuif is developed by means of potassium chromate/acetic acid (2 grams of K:Cr:O1 and 5 cos. of 30% acetic acid in 1 litre of water), followed by soaping at the boil.

The following examples illustrate the invention, without limiting it thereto:

Example 1 A printing paste of one of the following dyestufis :N-dihydro-1.2.1'.2'-anthraquinone azine; the hydroxy-derivative of the dyestufi' Colour Index No. 1109; 3.3'-dichloro-N-dihydro-l.2.1'.2'- anthraquinone azine; dibenzanthrone (Colour Index No. 1099) which has been prepared according to the method as described under (e), yields considerably better fixing and stronger printings than the corresponding printing pastes without the addition of thionyldiglycol. In case the steaming of the printed material is not immediately accomplished, but after some hours hanging, no considerable decline of the strength of the printings can be observed, that is, the stability of the printing color can also be observed on the printed material.

Valuable printing preparations may likewise be obtained by applying the methods described under (a) to (d) to the above named dyestuffs. The latter are especially suitable for the method of printing without previous reduction.

Example 2 The dyestuffs named in Example 1 may be replaced by the following dyestuifsz-B-methoxy- 3-hydroxy thionaphthene+4 methyl-B-bromo- 2.3 -'dihydro 3 ketothionaphthene-2- (para-dimethylamino) anile, 6.6 diethoxy-2.2'-bisthionaphtheneindigo, 6.6-dichloro-4.4'-dimethyl-bisthionaphtheneindigo, brominated anthanthrone, dichloroisoviolanthrone, the carbazole of 4.5- dibenzoylamino-alpha-alpha-anthrimide.

Likewise, other dyestuffs of the indigoid and anthraquinoid series and also sulphur dyestuffs may be applied with advantage in the present process.

We claim:-

1. The process which comprises printing textile fibres with a printing paste comprising a vat or sulphur dyestufi and thionyldiglycol.

2. The process which comprises printing textile fibres with a printing paste comprising a vat or sulphur dyestufi and thionyldiglycol in an amount between about 50 and about 100% of the dyestufi applied.

3. The process which comprises printing textile fibres with a printing paste comprising 3.3'-di chloro-N-dihydro-1.2.1'.2'-anthraquinone azine and thionyldiglycol in an amount between about 50 and about 100% "of the dyestufi applied.

4. The process which comprises printing textile fibres with a printing paste comprising dibenzanthrone and thionyldiglycol inan amount be- 6. A vat of sulphur dyestufi preparation for textile printing comprising thionyldiglycol.

7. A vat or sulphur dyestuff preparation comprising thionyldiglycol in an amount between about 50 and about 100% of the dyestufi present.

8. A vat dyestufi preparation comprising 3.3- dichloro-N-dihydro-1.2.1'.2-anthraquinone azine and thionyldiglycol in an amount between about '50 and about 100% of the dyestufi present.

9. A vat dyestufi preparation comprising dibenzanthrone and thionyldiglycol in an amount between about 50 and about 100% of the dyestufi present.

10. A vat dyestuff preparation comprising 6.6- diethoxy-2.2'-bisthionaphthene indigo and thionyldiglycol in an amount between about 50 and about 100% of the dyestuff present.

' HERMANN BERTHOLD.

ERWIN LIESE. 

